US8563784B2 - Catalytic method of manufacture of compounds of the diol type - Google Patents

Catalytic method of manufacture of compounds of the diol type Download PDF

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US8563784B2
US8563784B2 US13/140,089 US200913140089A US8563784B2 US 8563784 B2 US8563784 B2 US 8563784B2 US 200913140089 A US200913140089 A US 200913140089A US 8563784 B2 US8563784 B2 US 8563784B2
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US20110313204A1 (en
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Danilo Zim
Philippe Marion
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Rhodia Poliamida e Especialidades Ltda
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Rhodia Poliamida e Especialidades Ltda
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases

Definitions

  • the present invention relates to a catalytic method for the industrial-scale production of a compound of the diol type, such as 2-methylpentane-2-4-diol, also called 2,4-hexylene glycol, or HGL, from a ⁇ hydroxy carbonylated compound, notably diacetone-alcohol, or DAA.
  • a compound of the diol type such as 2-methylpentane-2-4-diol, also called 2,4-hexylene glycol, or HGL
  • HGL 2,4-hexylene glycol
  • DAA diacetone-alcohol
  • HGL is prepared industrially by catalytic hydrogenation of DAA, and Raney nickel is the catalyst most used, generally in considerable proportions, notably 5-20 wt. % relative to the weight of the DAA to be hydrogenated.
  • the Raney nickel must generally be washed, notably with distilled or demineralized water, for several days, before it is used in the hydrogenation reaction, so as to lower its basicity, in order to increase the selectivity of the reaction. This step is long and restricting and it would be highly desirable to omit it, for the economic and industrial interest of this reaction.
  • the applicant has found a completely unexpected way of avoiding the drawbacks mentioned above while obtaining excellent selectivity of the hydrogenation reaction on the ⁇ hydroxy carbonylated compounds, moreover without needing a long step of catalyst washing beforehand.
  • the present invention thus relates firstly to a method of preparing a compound of formula (IV) by a reaction of catalytic hydrogenation of a compound of formula (III), said compound of formula (III) being obtained by a reaction of base catalysed aldolization, characterized in that said hydrogenation reaction is catalysed by a Raney catalyst that has been pretreated with at least one buffer compound enabling said hydrogenation reaction to be maintained at a pH between 6 and 8 inclusive;
  • R 1 is a radical with from 1 to 10 carbon atoms
  • R 2 is a hydrogen atom or a radical with from 1 to 10 carbon atoms
  • R 3 is a hydrogen-atom or a radical with from 1 to 10 carbon atoms
  • X is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a vinyl group.
  • the present invention thus relates to a method of preparing a compound of formula (IV) by a reaction of catalytic hydrogenation of a compound of formula (III) notably comprising at least the following steps:
  • step b) a step of pretreatment of the Raney catalyst with at least one buffer compound for maintaining a pH between 6 and 8 during the hydrogenation reaction of step b);
  • the present invention relates more particularly to a method of preparing 2-methylpentane-2-4-diol (HGL) by a reaction of catalytic hydrogenation of diacetone-alcohol (DAA), characterized in that the reaction is catalysed by a Raney catalyst pretreated with a buffer compound enabling said reaction to be maintained at a pH between 6 and 8 inclusive.
  • DAA diacetone-alcohol
  • the present invention also relates to a compound of formula (IV) that can be obtained by the aforementioned method.
  • the radical can have from 1 to 10 carbon atoms and can be linear or branched, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic.
  • the radical can be a hydrocarbon radical.
  • the radical can comprise heteroatoms, such as O, F and/or N. We may mention for example the following radicals: methyl, ethyl, propyl, phenyl, trifluoromethyl, methoxy, and ethoxy.
  • alkyl group notably for the definition of radical X, a methyl, isobutyl, and ethyl.
  • radical X a phenyl, methylphenyl, and hydroxyphenyl radical.
  • alkoxy group notably for the definition of radical X, a methoxy, ethoxy, and isobutoxy radical.
  • radical X It is possible for example to use a vinyl group for the definition of radical X.
  • the compound of formula (III) is a ⁇ hydroxy carbonylated compound possessing an alcohol function on the ⁇ carbon of the carbonyl function, such as an aldehyde, ketone or ester function.
  • ⁇ hydroxy carbonylated compound of the present invention we may mention the following compounds: diacetone-alcohol (DAA), hydroxy-3 propanal, hydroxy-3 butanal, keto-3 hydroxy-5 methyl-5 heptane, hydroxy-3 ethyl-2 hexanal, and hydroxy-3 dihydrocinnamic aldehyde.
  • the compounds of formula (III) are notably obtained by a reaction of base catalysed aldolization between a compound of formula (I) (R 1 )(R 2 )C ⁇ O with a compound of formula (II) R 3 —CH 2 —COX.
  • the compound of formula (II) can be an ester, a ketone, or an aldehyde; i.e. an enolizable compound, possessing at least one hydrogen atom on the ⁇ carbon of the CO, in the reaction of base catalysed aldolization.
  • compound of formula (IV) we may mention for example as compound of formula (IV), the following compounds: methyl-2 pentanediol-2,4 (HGL), propanediol-1,3, butanediol-1,3, ethyl-2 hexanediol-1,3, methyl-5 heptanediol-3,5, and phenyl-1 propanediol-1,3.
  • HGL methyl-2 pentanediol-2,4
  • the present invention therefore consists of treating the catalyst by bringing it in contact with a buffer compound, before carrying out the hydrogenation reaction.
  • buffer means a compound capable of approximately maintaining a pH between 6 and 8 during the hydrogenation reaction.
  • the reaction of the invention can be carried out continuously or discontinuously.
  • the reaction can be carried out at a temperature between 70 and 150° C.
  • the reaction can be carried out at a pressure between 5 and 50 bar, notably between 10 and 25 bar.
  • the reaction time, for synthesizing an optimum amount of the compound of formula (IV), can be between 5 minutes and 5 hours.
  • the hydrogenation reaction is notably carried out in the liquid phase.
  • the hydrogen can notably be dissolved wholly or partly in the compound of formula (III).
  • the reaction can notably be carried out in a continuous reactor, perfectly stirred for the liquid phase.
  • the gas can be introduced either by systems of plunger tubes or by means of an auto-suction turbine or any other means, for example with an external recirculating loop. It is also possible to use a continuous reactor of the piston type such as a bubble column or a reactor with venturi ejector.
  • buffer compound Generally from 0.01 to 2 wt. % of buffer compound is used, relative to the weight of the compound of formula (III). Generally from 0.1 to 20 wt. % of buffer compound is used, relative to the weight of the catalyst.
  • the Raney catalyst according to the invention can be a Raney nickel, a Raney cobalt or a Raney copper. These porous catalysts are well known and are generally called skeletal catalysts or sponge catalysts.
  • Raney nickel is a solid catalyst used in numerous industrial processes. It is notably used as a heterogeneous catalyst for a great variety of reactions in organic chemistry, most often for hydrogenation reactions.
  • Raney nickel is made by treating a powder of nickel-aluminium alloy with concentrated soda. In the course of this treatment, called “activation”, most of the aluminium of the alloy is dissolved, with parallel evolution of much hydrogen.
  • the resultant porous structure has a very high specific surface of 100 m 2 /g, which contributes to its efficiency as a catalyst.
  • Buffer compound means, according to the invention, a solution containing an acid and its conjugated base, which has the property of not allowing its pH to change significantly despite addition of a base or of an acid to the medium.
  • the solution generally has an acid/base concentration ratio between 0.01 and 100.
  • organic or inorganic buffer compounds mentioned in the following documents: Good, N. E., et al. (1966) Hydrogen Ion Buffers for Biological Research. Biochemistry 5(2), 467-477; CRC Handbook of Chemistry and Physics, CRC Press Inc. David R. Lide, 1992-1993, 73rd edition, pages 8-37-8-42.
  • the buffer compound according to the invention can be selected from the group consisting of:
  • one or more buffer agents can be used during the reaction.
  • the pretreatment can be carried out by mixing the catalyst with the buffer compound for a time generally between 1 hour and 24 hours. Mixing can be carried out without particular stirring and at room temperature.
  • the buffer can be in liquid form and the catalyst can be in the form of powder.
  • the catalyst thus pretreated is then brought in contact with the reaction mixture of the present invention.
  • a mixture is discharged comprising the compound of formula (III), the compound of formula (IV), the catalyst and some by-products.
  • the catalyst can be separated from the organic products by any means of solid/liquid separation, for example a filter or a decanter.
  • the liquid obtained can notably be sent to a distillation column for separating the compound of formula (III) and the compound of formula (IV).
  • An autoclave reactor with a capacity of 150 ml is charged with DAA (80 g), Raney nickel (8 g) and optionally variable amounts of buffer.
  • the Raney nickel catalyst can be washed with distilled water for a week to lower the basicity of the catalyst. This is the procedure used conventionally for Raney nickel catalysts in the reaction of hydrogenation of DAA.
  • the catalyst can also be pretreated beforehand by mixing it with KH 2 PO 4 for some hours.
  • the autoclave is sealed, and then purged with nitrogen and with hydrogen.
  • the autoclave is then placed under hydrogen pressure at 20 bar and heated to a temperature of 100° C. Magnetic stirring is carried out at 1500 revolutions per minute.
  • the data of the reaction such as temperature, pressure, hydrogen consumption, reaction time and conversion are measured or calculated throughout the reaction.
  • the reactor is cooled and a sample is measured by gas chromatography and characterized using a mass spectrometer.
  • the selectivity S of a chemical reaction specifies the amount of desired product formed relative to the number of moles of the limiting reactant consumed. It indicates whether several reactions take place in parallel, leading to unwanted by-products, or whether the required reaction is the only one consuming the reactant.
  • the percentage of KH 2 PO 4 is expressed by weight relative to the weight of the catalyst.
  • test C1 the catalyst was washed with distilled water for 7 days. It is observed that the selectivity is inadequate, owing to formation of IPA.
  • test C2 the catalyst was not washed with water beforehand but was pretreated with an aqueous solution containing acetic acid to obtain a pH of 7. The selectivity observed is very poor owing to massive formation of IPA.
  • test C3 the catalyst was neither washed nor pretreated. Only KH 2 PO 4 was added to the reaction mixture. Very poor selectivity is still observed.
  • test 1 the unwashed catalyst was pretreated with KH 2 PO 4 . Very good selectivity is observed.
  • test 2 the catalyst was washed and pretreated. An equivalent selectivity was observed. It thus appears that pretreatment of the catalyst with a buffer according to the present invention makes it possible not only to obtain excellent selectivity, but also to eliminate a step of preliminary washing of the catalyst.
  • reaction is carried out in the same way as in example 1 but in the presence of 0.5 wt. % of Raney nickel relative to the weight of DAA.
  • the percentage of KH 2 PO 4 is expressed by weight relative to the weight of the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US13/140,089 2008-12-16 2009-12-15 Catalytic method of manufacture of compounds of the diol type Active 2030-05-23 US8563784B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR0858651A FR2939790B1 (fr) 2008-12-16 2008-12-16 Procede catalytique de fabrication de composes de type diol
FR0858651 2008-12-16
FRFR0858651 2008-12-16
PCT/IB2009/007760 WO2011077176A1 (fr) 2008-12-16 2009-12-15 Procede catalytique de fabrication de composes de type diol

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US20110313204A1 US20110313204A1 (en) 2011-12-22
US8563784B2 true US8563784B2 (en) 2013-10-22

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US (1) US8563784B2 (fr)
EP (1) EP2379477B1 (fr)
JP (1) JP2012512263A (fr)
CN (1) CN102256918B (fr)
BR (1) BRPI0918127B8 (fr)
FR (1) FR2939790B1 (fr)
WO (1) WO2011077176A1 (fr)

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Publication number Priority date Publication date Assignee Title
US8710278B1 (en) 2013-01-31 2014-04-29 Eastman Chemical Company Process for producing polyols
US9056824B2 (en) 2013-01-31 2015-06-16 Eastman Chemical Company Preparation of hydroxy aldehydes
CN109836398B (zh) * 2017-11-27 2021-08-17 荆楚理工学院 一种特殊生物缓冲剂—哌嗪二乙磺酸1.5Na盐的制备方法
EP3747855B1 (fr) * 2019-06-04 2024-01-10 OQ Chemicals GmbH Procédé de fabrication continue de dioles à partir des aldéhydes au moyen du catalyseur cobalt de raney

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0920703A (ja) 1995-07-07 1997-01-21 Mitsubishi Gas Chem Co Inc １，３−プロパンジオールの製法
US6969780B1 (en) * 2004-12-20 2005-11-29 Lyondell Chemical Technology, L.P. Production of butanediol

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB660177A (en) * 1948-07-08 1951-10-31 British Celanese Manufacture of 2-methyl-1,3-pentane diol
DE2917752C2 (de) * 1979-05-02 1982-07-01 Kawaken Fine Chemicals Co., Ltd., Tokyo Katalysator zur stereoselektiven Reduktion von Carbonylverbindungen und Verwendung des Katalysators
FI95690C (fi) * 1993-09-07 1996-03-11 Neste Oy Menetelmä 2-etyyli-1,3-heksaanidiolin valmistamiseksi

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0920703A (ja) 1995-07-07 1997-01-21 Mitsubishi Gas Chem Co Inc １，３−プロパンジオールの製法
US6969780B1 (en) * 2004-12-20 2005-11-29 Lyondell Chemical Technology, L.P. Production of butanediol

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
International Search Report issued on Mar. 29, 2010, by the European Patent Office as the International Searching Authority in International Patent Application No. PCT/IB2009/007760.
Kandegedara et al., "Noncomplexing Tertiary Amines as "Better" Buffers Covering the Range of pH 3-11. Temperature Dependence of Their Acid Dissociation Constants," Analytical Chemistry, Aug. 1, 1999, pp. 3140-3144, vol. 71, No. 15.
Mozingo, "Catalyst, Raney Nickel, W-2," Organic Syntheses, 1941, p. 15, vol. 21.
Written Opinion of the International Searching Authority (Form PCT/ISA/237) issued on Oct. 4, 2011, in International Patent Application No. PCT/IB2009/007760.

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Publication number Publication date
WO2011077176A1 (fr) 2011-06-30
US20110313204A1 (en) 2011-12-22
EP2379477B1 (fr) 2017-07-05
JP2012512263A (ja) 2012-05-31
FR2939790A1 (fr) 2010-06-18
FR2939790B1 (fr) 2013-07-12
CN102256918A (zh) 2011-11-23
BRPI0918127B1 (pt) 2018-02-14
CN102256918B (zh) 2014-07-16
EP2379477A1 (fr) 2011-10-26
BRPI0918127B8 (pt) 2022-12-13
BRPI0918127A2 (pt) 2015-11-24

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